Photovoltaic device including a P-N junction and method of manufacturing

ABSTRACT

A photovoltaic device includes a substrate structure and a p-type semiconductor absorber layer, the substrate structure including a CdSSe layer. A photovoltaic device may alternatively include a CdSeTe layer. A process for manufacturing a photovoltaic device includes forming a CdSSe layer over a substrate by at least one of sputtering, evaporation deposition, CVD, chemical bath deposition process, and vapor transport deposition process. The process includes forming a p-type absorber layer above the CdSSe layer.

FIELD OF THE INVENTION

Disclosed embodiments relate generally to photovoltaic devices and, in particular, to photovoltaic devices having a p-n junction.

BACKGROUND OF THE INVENTION

A photovoltaic structure generates electrical power by converting light into direct current electricity using semiconductor materials that exhibit the photovoltaic effect. The photovoltaic effect generates electrical power upon exposure to light as photons, packets of energy, are absorbed within the semiconductor to excite electrons to a higher energy state. These excited electrons are thus able to conduct and move freely within the material. When an electron is displaced within the material, a ‘hole’ forms where the electron was previously bound to a particular atom of the material.

A basic unit of photovoltaic structure, commonly called a cell, may generate only small scale electrical power. Thus, multiple cells may be electrically connected to aggregate the total power generated among the multiple cells within a larger integrated device, called a module, or a panel. A photovoltaic module may further comprise a protective back layer and encapsulant materials to protect the included cells from environmental factors. Multiple photovoltaic modules or panels can be assembled together to create a photovoltaic system, or array, capable of generating significant electrical power up to levels comparable to other types of utility-scale power plants. In addition to photovoltaic modules, a utility-scale array would further include mounting structures, electrical equipment including inverters, transformers, and other control systems. Considering various levels of device, from individual cell to utility-scale arrays containing a multitude of modules, all such implementations of the photovoltaic effect may contain one or more photovoltaic structures to accomplish the energy conversion.

To generate power from sunlight, the active area of a photovoltaic structure or device generally includes a bi-layer of two distinct regions, one above the other and each containing one or more materials, where each material may further contain added impurities. The result is that one region in the photovoltaic device is n-type, having an excess of negatively charged electrons, while the other is p-type, having an excess of positively charged holes. These regions are commonly named the window layer, for the n-type region, and the absorber layer, for the p-type region. Where these two regions abut one another, a p-n junction is formed. The window layer is preferred to be as thin as possible in order to allow the maximum amount of light to reach the absorber layer, yet it also needs to be sufficiently thick to maintain a robust p-n junction with the absorber layer.

When photons create free electrons and holes, collectively called charge carriers, near the p-n junction, the internal electric field of the junction causes the electrons to move towards the n side of the junction and the holes towards the p side thereby generating an electrical charge potential. A front contact, electrically connected to the window layer, and a back contact, electrically connected to the absorber layer can provide pathways through which the electrical charge potential can flow to become an electrical current. Electrons can flow back to the p-side via an external current path, or circuit.

When two or more separate materials are used to create the p-n junction, the interface or interfaces between the materials can affect the efficient performance of the photovoltaic device. Where the materials have formed crystalline grains, the grain boundary separating the two abutting materials can scatter the electrons and holes and prevent them from flowing across the p-n junction. While moving within the material where generated, such as may occur after being scattered by a grain boundary, mobile electrons and holes may recombine. This reduces the total number of charge carriers available to generate current flow within the device and the overall conversion efficiency. Efficiency, in this instance, refers to the electrical power or energy generated by the PV device compared to the equivalent energy of photons incident on the device.

The manufacturing of a photovoltaic structure generally includes sequentially forming the functional layers through process that may include vapor transport deposition, atomic layer deposition, chemical bath deposition, sputtering, closed space sublimation, or any other suitable process that creates the desired material. Once a layer is formed it may be desirable to modify the physical characteristics of the layer through subsequent activation processes. For example, an activation step may include passivation, which is defect repair of the crystalline grain structure, and may further include annealing. Imperfections or defects in the crystalline grain disrupt the periodic structure in the layer and can create areas of high resistance or current loss.

An activation process may accomplish passivation through the introduction of a chemical dopant to the semiconductor bi-layer as a bathing solution, spray, or vapor. Subsequently annealing the layer in the presence of the chemical dopant at an elevated temperature provides grain growth and incorporation of the dopant into the layer. The larger grain size reduces the resistivity of the layer, allowing the charge carriers to flow more efficiently. The incorporation of a chemical dopant may also make the regions of the bi-layer more n-type or more p-type and able to generate higher quantities of mobile charge carriers. Each of these improves efficiency by increasing the maximum voltage the device can produce and reducing unwanted electrically-conductive regions.

In the above activation process, the summary parameters of anneal temperature, chemical bath composition, and soak time, for a particular layer depend on that layer's material and may have adverse effects on other layers present in the photovoltaic structure. For example, during the activation step of the absorber layer, the high temperature anneal may cause the window layer to flux into and intermix with the absorber layer, which can lead to the window layer having a non-uniform thickness or becoming discontinuous, which decreases device performance. It would be desirable to use more chemically potent doping solution, higher annealing temperatures, or longer anneal duration in an activation step to more aggressively treat the absorber layer, as this would increase the benefits conferred on the absorber layer by the activation step. However, using more aggressive process conditions during the activation step can cause more fluxing, thus further degrading or destroying the window layer, which decreases device performance.

This problem cannot be solved by simply increasing the initial thickness of the window layer so that if some of the material is fluxed away during the activation step, enough remains to maintain a good junction. This apparent remedy causes other problems as the window layer will absorb some photons and having a thicker window layer after the activation step reduces the available light for photon harvesting at the absorber layer. In general, it is desired to have a very thin window layer to provide better light transmission to the absorber layer.

Therefore, it is desirable to provide an efficient p-n junction between layers of different semiconductor materials, incorporating an absorber layer that can be activated with an aggressive activation step while maintaining the integrity of a thin window layer, and a method of making such a photovoltaic structure.

BRIEF DESCRIPTION OF THE DRAWINGS

The above, as well as other advantages of the present invention, will become readily apparent to those skilled in the art from the following detailed description of a preferred embodiment when considered in the light of the accompanying drawings in which:

FIG. 1 depicts a schematic of functional layers in a typical prior art photovoltaic device.

FIG. 2 depicts a schematic of functional layers in a first embodiment of a photovoltaic device.

FIG. 3 depicts a schematic of functional layers in a second embodiment of a photovoltaic device.

FIG. 4 depicts a schematic of functional layers in a third embodiment of a photovoltaic device.

FIG. 5 depicts a schematic of functional layers in a fourth embodiment of a photovoltaic device.

FIG. 6 depicts a schematic of functional layers in a fifth embodiment of a photovoltaic device.

FIG. 7 depicts a schematic of functional layers in a sixth embodiment of a photovoltaic device.

FIG. 8 depicts a process for manufacturing a photovoltaic device.

FIG. 9 depicts an expanded step of a process for manufacturing a layer in a photovoltaic device.

FIG. 10 depicts a schematic of functional layers in a seventh embodiment of a photovoltaic device.

FIG. 11 depicts a schematic of functional layers in a eighth embodiment of a photovoltaic device.

FIG. 12 depicts a schematic of functional layers in a ninth embodiment of a photovoltaic device.

FIG. 13 depicts a schematic of functional layers in a tenth embodiment of a photovoltaic device.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

The following detailed description and appended drawings describe and illustrate various exemplary embodiments of the invention. The description and drawings serve to enable one skilled in the art to make and use the invention and are not intended to limit the scope of the invention in any manner. In respect of the methods disclosed, the steps presented are exemplary in nature and, thus, the order of the steps is not necessary or critical.

Photovoltaic devices generally comprise multiple layers of material. FIG. 1 depicts a typical photovoltaic device 100. Photovoltaic device 100 may include a base layer 105, a transparent conductive oxide (TCO) layer 110, a window layer 115 made from an n-type cadmium sulfide (CdS) semiconductor material, an absorber layer 120 made from a p-type cadmium telluride (CdTe) semiconductor material, and a metal back contact 125. Photovoltaic devices may further include electrical connections, not shown, that provide a current path to communicate generated current flow, such as from one photovoltaic cell to adjacent cells in a module or from one photovoltaic module to adjacent modules in an array. Alternatively, the electrical connections may communicate the current flow to an external load device where the photogenerated current provides power.

Each of the layers described in the following embodiments may be composed of more than one layer or film. Additionally, each layer can cover all or a portion of the device and/or all or a portion of the layer or material underlying the layer. For example, a “layer” can mean any amount of material that contacts all or a portion of a surface. During a process to form one of the layers, the created layer forms on an outer surface, typically a top surface, of a substrate or substrate structure. A substrate structure may include a base layer introduced into a deposition process and any other or additional layers that may have been deposited onto the base layer in a prior deposition process. Layers may be deposited over the entirety of a substrate with certain portions of the material later removed through laser ablation, scribing, or other material-removal process.

Several specific embodiments of a novel photovoltaic device will be described with reference to the figures. The novel photovoltaic device according to the disclosed embodiments can include material compositions, or interfacial layers to achieve high performance efficiency in the p-n junction. In a first embodiment of a photovoltaic device 200 according to the present disclosure as depicted in FIG. 2, an n-type window layer 230 comprising cadmium sulphoselenide (CdSSe) is deposited over a substrate structure including a base layer 205 and a TCO layer 210. A p-type absorber layer 220 is deposited over the CdSSe layer 230. The CdSSe layer 230 and the p-type absorber layer 220 form a p-n junction in the photovoltaic device 200. A metal back contact 225 is formed over the p-type absorber layer 220.

The base layer 205 may include glass, for example, soda lime glass or float glass. Alternatively, the base layer 205 may include polymeric, ceramic, or other materials that provide a suitable structure for forming a base of photovoltaic cell. Preferably, the base layer 205 transmits light through its thickness with minimal or no absorption or reflection of photons. The base layer 205 may have additional layers applied (not shown) that promote the transmission of photons through its thickness, which may include anti-reflective coatings or anti-soiling coatings. The base layer 205 may have additional layers applied (not shown) that promote the chemical stability of the glass, which may include buffer or barrier layers that inhibit the diffusion of chemical ions from, into, or across the glass substrate. The base layer 205 provides a substrate surface upon which further layers of material are formed to create the photovoltaic device.

The TCO layer 210 allows light to pass through to a semiconductor window layer 215 while serving as an ohmic electrode to transport photogenerated charge carriers away from the light absorbing material. The TCO layer 210 may include tin oxide, zinc oxide, cadmium stannate, doped variations thereof, or any other suitable material. The TCO layer 210 can be formed over the base layer 205 through various deposition methods including chemical vapor deposition, molecular beam deposition, sputtering, spray pyrolysis, and other conventional methods.

A metal back contact 225 is provided opposite to the TCO layer 210, sandwiching the semiconductor layers of the photovoltaic device 200. The metal back contact 225 serves as a second ohmic electrode to transport photogenerated charge carriers. The metal back contact 225 can include electrically conductive materials, such as metallic silver, nickel, copper, aluminum, titanium, palladium, chrome, molybdenum, gold, or combinations thereof. The metal back contact 225 can be formed on the semiconductor layers through various deposition methods including chemical vapor deposition, molecular beam deposition, sputtering, spray pyrolysis, and other conventional methods.

The TCO layer 210 may form or may be electrically connected to a front contact. The metal back contact 225 may form or may be electrically connected to a back contact. The front contact forms a current path through which the electrical current generated by the active layers of the photovoltaic device may flow. The back contact forms a second current path through which generated current may flow. The front contact may connect one photovoltaic cell to an adjacent cell in one direction within a photovoltaic module or, alternatively, to a terminal of the photovoltaic module. Likewise, the back contact may connect the photovoltaic cell to a terminal of the photovoltaic module or, alternatively, to an adjacent cell in a second direction within the photovoltaic module, forming a series configuration. The front contact or back contact may connect the photovoltaic cell to an external terminal of the photovoltaic module in which it is located.

According to this first embodiment, the n-type CdSSe layer 230 forms the window layer, that is, the n-type region of the p-n junction within the photovoltaic device 200. The thickness of the CdSSe layer 230 can be between 10 nm to 100 nm thick or alternatively between 30 nm and 75 nm thick. The CdSSe layer 230 may be composed of cadmium, sulfur and selenium in varying amounts to form a CdSS_(1−x)Se_(x) compound, where x is in the range of about 1 to 25 at %, or alternatively between about 5 to 10 at %. The compositional ratio (at %) of a compound, for example CdS_(1−x)Se_(x), is determined by comparing the number of sulfur atoms and the number of selenium atoms in a given amount of the compound with the total sum of sulfur and selenium atoms in the given amount. For example, where x=10 at %, there are 9 sulfur atoms for every 1 selenium atom in a given amount of CdS_(90%)Se_(10%) compound.

The CdSSe layer 230 can be manufactured by a deposition process, such as vapor transport deposition, atomic layer deposition, chemical bath deposition, sputtering, closed space sublimation, or any other suitable process. In forming the CdSSe layer 230 using a process requiring the evaporation of powder, such as vapor transport deposition, the CdSSe layer 230 may be formed from the co-evaporation of a blended mixture of CdS and cadmium selenide (CdSe) powder, or the evaporation of a pre-alloyed CdSSe powder. The composition of the blended powders for co-evaporation or the composition of a pre-alloyed powder can be tailored so that the as-deposited film achieves the desired CdS_(1−x)Se_(x) compositional ratio. Alternatively, a CdSSe layer may be formed by sequentially depositing a CdS layer followed by depositing a CdSe layer with a subsequent annealing or heat treatment process to allow alloying of the two layers to achieve the desired CdS_(1−x)Se_(x) compositional ratio. The annealing or heat treatment process may be a separate step in a manufacturing process or may occur concurrently with the subsequent deposition of a further layer of the photovoltaic device, for example the deposition of the p-type absorber layer 220.

Although the disclosed embodiments may describe a CdSSe layer as a single layer within the device, in each case the CdSSe layer may comprise multiple layers of CdSSe of varying composition to form a continuous or step-wise gradient of the sulfur to selenium ratio. For example, the CdSSe layer 230 may be formed as a single layer of CdS_(1−x)Se_(x) where x is held constant throughout the formation process. Alternatively, the CdSSe layer 230 may be formed sequentially as multiple layers of CdS_(1−x)Se_(x) where x varies in value for each of the sequentially formed layers. For example, a first CdS_(1−x)Se_(x) layer may be deposited where x=5 at %, and a second CdS_(1−x)Se_(x) layer may be deposited where x=10 at %. These two adjacent layers may together form the CdSSe layer 230. As a further alternative, the ratio of sulfur to selenium may be varied continuously throughout the formation process so that, for example, the composition of the formed CdS_(1−x)Se_(x) layer at a first end is x=5 at % and at a second end is x=10 at %, and where x varies continuously from 5 at % to 10% between the first and second ends. The whole of the formed layer having the continuous gradient may form the CdSSe layer 230.

The p-type absorber layer 220 may include a p-type semiconductor material to form the p-type region of the p-n junction within the photovoltaic device 200. The absorber layer 220 preferably absorbs photons passing through from the CdSSe window layer 230 to mobilize charge carriers. The absorber layer 220 may be formed of CdTe. An absorber layer 220 formed of CdTe may further include impurities or dopants in the CdTe bulk material. The absorber layer 220 may be between 500 nm to 8000 nm thick, or alternatively between 1000 nm to 3500 nm thick. The absorber layer 220 may be formed over the CdSSe window layer 230 by a deposition process, such as vapor transport deposition, atomic layer deposition, chemical bath deposition, sputtering, closed space sublimation, or any other suitable process. In the following alternative embodiments, similar layers as those described in the first embodiment are included and similarly numbered (incremented by 100).

In a second embodiment of a photovoltaic device 300, as depicted in FIG. 3, an interfacial layer of CdSSe 330 is deposited over a substrate structure including a base layer 305, TCO layer 310, and a CdS window layer 315. A p-type absorber layer of CdTe 320 is deposited over the CdSSe layer 330. The CdS window layer 315 and the CdSSe layer 330 together form the n-type region of the p-n junction with the p-type CdTe absorber layer 320. A metal back contact 325 is formed over the p-type CdTe layer 320. According to this second embodiment, the CdSSe interfacial layer 330 is formed of similar structure and using similar methods as the CdSSe window layer 230 in the previous embodiment. The CdS window layer 315 may be formed of a cadmium sulfide material that further includes impurities or dopants in the CdS bulk material. The CdS window layer 315 may be between 10 nm to 100 nm thick or alternatively between 30 nm to 75 nm thick. The CdS window layer 315 may be formed over the TCO layer 310 by a deposition process, such as vapor transport deposition, atomic layer deposition, chemical bath deposition, sputtering, closed space sublimation, or any other suitable process.

In a third embodiment of a photovoltaic device 400, as depicted in FIG. 4, an n-type CdSSe window layer 430 is deposited over a substrate structure including a base layer 405 and a TCO layer 410. A cadmium sulphotelluride (CST) p-type absorber layer 435 is deposited over the CdSSe layer 430. A metal back contact 425 is formed over the p-type CST absorber layer 435. The CST absorber layer 435 may be composed of cadmium sulfur and tellurium in varying amounts to form a CdS_(x)Te_(1−x) compound, where x may be between 1 to 30 at %, or alternatively between 1 to 15 at %, or further alternatively between 2 to 10 at %. A CST absorber layer 435 may be between 500 to 8000 nm thick, or alternatively between 1000 nm to 3500 nm thick. A CST layer may be formed by a deposition process, such as vapor transport deposition, atomic layer deposition, chemical bath deposition, sputtering, closed space sublimation, or any other suitable process.

In a fourth embodiment of a photovoltaic device 500, as depicted in FIG. 5, an n-type window layer of CdSSe 530 is deposited over a substrate structure including a base layer 505 and a TCO layer 510. A CST interfacial layer 535 is deposited over the n-type CdSSe window layer 530. A p-type CdTe absorber layer 520 is deposited over the CST interfacial layer 535. The CST interfacial layer 535 may be similarly composed of CdS_(x)Te_(1−x), where x may be between 1 to 30 at %, or alternatively between 1 to 15 at %, or further alternatively between 2 to 10 at %. However, a CST interfacial layer 535 adjacent to the CdTe absorber layer 520 may be between 20 nm to 1000 nm thick, or alternatively may be between 400 nm to 600 nm thick. The CST interfacial layer 535 and the p-type CdTe absorber layer 520 together form the p-type region of the p-n junction with the n-type CdSSe window layer 530. A metal back contact 525 is formed over the p-type CdTe layer 520.

In a fifth embodiment of a photovoltaic device 600, as depicted in FIG. 6, a CdSSe interfacial layer 630 is deposited over a substrate structure including a base layer 605, a TCO layer 610, and an n-type CdS window layer 615. A p-type CST absorber layer 635 is deposited over the CdSSe interfacial layer 630. The CdS window layer 615 and the CdSSe interfacial layer 630 together comprise the n-type region to form a p-n junction with the p-type CST absorber layer 635. A metal back contact 625 is formed over the p-type CdTe layer 620.

In a sixth embodiment of a photovoltaic device 700, as depicted in FIG. 7, a CdSSe interfacial layer 730 is deposited over a substrate structure including a base layer 705, a TCO layer 710 and an n-type CdS window layer 715. A CST interfacial layer 735 is deposited over the CdSSe interfacial layer 730. A p-type CdTe absorber layer 720 is deposited over the CST interfacial layer 735. The p-type CdTe absorber layer 720 and the CST interfacial layer 735 together comprise the p-type region to form a p-n junction with the n-type CdS window layer 715 and the CdSSe interfacial layer 730, which together comprise the n-type region. A metal back contact 725 is formed over the p-type CdTe absorber layer 720.

According to a seventh embodiment of a photovoltaic device 1000, as depicted in FIG. 10, a TCO layer 1010 is formed on a base layer 1005. A p-type cadmium selenide telluride (CdSeTe) layer 1040 is formed over the TCO layer 1010. The TCO layer 1010 may include a material doped to be n-type in order to form a p-n junction with the p-type CdSeTe layer 1040. A metal back contact 1025 is formed over the p-type CdSeTe layer 1040.

The CdSeTe layer 1040, as a p-type absorber layer, preferably absorbs the photons passing through from the base layer 1005 and TCO layer 1010 to mobilize charge carriers. The thickness of the CdSeTe layer 1040 can be between about 2000 nm to 4000 nm thick or alternatively between about 2500 nm and 3500 nm thick. The CdSeTe layer 230 may be composed of cadmium, selenium, and tellurium in varying amounts to form a CdSe_(x)Te_(1−x) compound, where x is in the range of about 1 to about 25 at %, or alternatively between about 5 to about 20 at %. The compositional ratio (at %) of a compound, for example CdSe_(x)Te_(1−x), is determined by comparing the number of selenium atoms and the number of tellurium atoms in a given amount of the compound with the total sum of selenium and tellurium atoms in the given amount. For example, where x=10 at %, there are 9 tellurium atoms for every 1 selenium atom in a given amount of CdSe_(10%)Te_(90%) compound.

The CdSeTe layer 1040 can be manufactured by a deposition process, such as vapor transport deposition, atomic layer deposition, chemical bath deposition, sputtering, closed space sublimation, or any other suitable process. In forming the CdSeTe layer 1040 using a process requiring the evaporation of powder, such as vapor transport deposition, the CdSeTe layer 1040 may be formed from the co-evaporation of a blended mixture of CdSe and CdTe powder, or the evaporation of a pre-alloyed CdSeTe powder. The composition of the blended powders for co-evaporation or the composition of a pre-alloyed powder can be tailored so that the as-deposited film achieves the desired CdSe_(x)Te_(1-x) compositional ratio. Alternatively, a CdSeTe layer may be formed by sequentially depositing a CdSe layer followed by depositing a CdTe layer with a subsequent annealing or heat treatment process to allow alloying of the two layers to achieve the desired CdSe_(x)Te_(1−x) compositional ratio. The annealing or heat treatment process may be a separate step in a manufacturing process or may occur concurrently with the subsequent deposition or annealing of a further layer of the photovoltaic device, for example the deposition of a metal back contact layer 1025 or annealing of CdTe absorber layer.

Although the disclosed embodiments may describe a CdSeTe layer as a single layer within the device, in each case the CdSeTe layer may comprise multiple layers of CdSeTe of varying composition to form a continuous or step-wise gradient of the selenium to tellurium ratio. For example, the CdSeTe layer 1040 may be formed as a single layer of CdSe_(x)Te_(1-x) where x is held constant throughout the formation process. Alternatively, the CdSeTe layer 1040 may be formed sequentially as multiple layers of CdSe_(x)Te_(1−x) where x varies in value for each of the sequentially formed layers. For example, a first CdSe_(x)Te_(1−x) layer may be deposited where x=5 at %, and a second CdSe_(x)Te_(1−x) layer may be deposited where x=10 at %. These two adjacent layers may together form the CdSeTe layer 1040. As a further alternative, the ratio of selenium to tellurium may be varied continuously throughout the formation process so that, for example, the composition of the formed CdSe_(x)Te_(1−x) layer at a first end is x=5 at % and at a second end is x=10 at %, and where x varies continuously from 5 at % to 10% between the first and second ends. The whole of the formed layer having the continuous gradient may form the CdSeTe layer 1040.

According to an eighth embodiment of a photovoltaic device 1100, as depicted in FIG. 11, a CdS window layer 1115 is formed over a TCO layer 1110 over the base layer 1105. A p-type CdSeTe layer 1140 is formed over the CdS window layer 1115. The CdS window layer 1115 forms a p-n junction with the p-type CdSeTe layer 1140. A metal back contact 1125 is formed over the p-type CdSeTe layer 1140.

According to a ninth embodiment of a photovoltaic device 1200, as depicted in FIG. 12, a TCO layer 1210 is formed over a base layer 1205. A cadmium sulfur selenide telluride (Cd(S,Se,Te)) layer 1242 is formed over the TCO layer 1210. A metal back contact 1225 is formed over the p-type CdSeTe layer 1242. The Cd(S,Se,Te) layer 1242 is formed from a compound of cadmium, sulfur, selenium, and tellurium, CdS_(y)Se_(x)Te_(1−(x+y)) where 0>y>1, or alternatively where 0.02<x<0.25 and 0.02<y<0.25, or as a further alternative, where 0.05<x<0.20 and 0.02<y<0.05. The Cd(S,Se,Te) layer 1242 is between about 2000 nm to about 4000 nm thick, or alternatively between about 2500 nm to about 3500 nm thick.

In one embodiment, the Cd(S,Se,Te) layer 1242 comprises multiple sub-layers where x and y vary to provide preferred concentrations a various points through the layer thickness. For example, in one embodiment both x and y may vary to provide a higher sulfur and selenium concentration adjacent to the TCO layer 1210, and decrease throughout the thickness of the layer moving away from the TCO layer 1210. In other alternative embodiments, the value of x or y or both may remain constant throughout the Cd(S,Se,Te) layer 1242 between the TCO layer 1210 and metal back contact 1225.

The Cd(S,Se,Te) layer 1242 can be manufactured by a deposition process, such as vapor transport deposition, atomic layer deposition, chemical bath deposition, sputtering, closed space sublimation, or any other suitable process. In forming the Cd(S,Se,Te) layer 1242 using a process requiring the evaporation of powder, such as vapor transport deposition, the Cd(S,Se,Te) layer 1242 may be formed from the co-evaporation of a blended mixture of CdS, CdSe, and CdTe powders, or the evaporation of a pre-alloyed Cd(S,Se,Te) powder. The composition of the blended powders for co-evaporation or the composition of a pre-alloyed powder can be tailored so that the as-deposited film achieves the desired CdS_(y)Se_(x)Te_(1−(x+y)) compositional ratio. Alternatively, a Cd(S,Se,Te) layer may be formed by sequentially depositing a CdS layer followed by depositing a CdSeTe layer, or various other combinations of compounds containing cadmium, sulfur, selenium and tellurium, with a subsequent annealing or heat treatment process to allow alloying of the two layers to achieve the desired CdS_(y)Se_(x)Te_(1−(x+y)) compositional ratio. The annealing or heat treatment process may be a separate step in a manufacturing process or may occur concurrently with the subsequent deposition of a further layer of the photovoltaic device, for example the deposition of the metal back contact 1225.

According to a tenth embodiment of a photovoltaic device 1300, as depicted in FIG. 13, a TCO layer 1310 is formed over a base layer 1305. An n-type CdS window layer 1315 is formed over the TCO layer 1310. A p-type CdSeTe layer 1343 is formed over the CdS window layer 1315. A p-type CdTe absorber layer 1320 is formed over the CdSeTe layer 1343. A metal back contact 1325 is formed over the CdTe layer 1320. In this embodiment the CdSeTe layer 1343 may have a similar composition to the CdSeTe layer 1040 described above, and may be between about 250 nm and about 2500 nm thick, or alternatively between about 400 nm to about 1500 nm thick. The CdTe layer 1320 may be between about 250 nm and about 3500 nm thick, or alternatively between about 500 nm to about 2500 nm thick. The thickness of the CdSeTe layer 1343 and the thickness of the CdTe absorber layer 1320 together may be selected to form a total thickness of about 2000 nm to about 4000 nm thick, or alternatively of about 2500 nm to about 3500 nm thick.

As depicted in FIG. 13, the CdSeTe layer 1343 may be formed over the CdS window layer 1315, with the CdTe absorber layer 1320 formed over the CdSeTe layer 1343. In a further alternative (not shown), the CdS window layer 1315 may be omitted from the photovoltaic device 1300. As an additional alternative (not shown), the CdTe absorber layer 1320 may be formed over the CdS window layer 1315, with the CdSeTe layer 1343 formed over the CdTe layer 1320.

As the window, absorber, or interfacial layer of a photovoltaic module, the CdS, CdTe, CST, CdSeTe, and combinations thereof, are crystalline solids that can be sequentially formed in thin films on a substrate structure that may include a base layer, TCO, and additional buffer layers, barrier layers and coatings. According to the disclosed embodiments, a layer of CdSSe can be introduced in place of or in addition to a layer of CdS in the n-type region of the p-n junction within a photovoltaic device that further includes a p-type CdTe or CST, or both, in the p-type region of the p-n junction. According to further disclosed embodiments, a layer of CdSeTe can be introduced in place of, or in addition to, CdS or CdTe layers within a photovoltaic device.

A method of manufacturing a photovoltaic structure, as depicted in FIG. 8, can include sequentially forming layers on a substrate. In a first step 802, a TCO layer can be formed on a base layer, such as glass. In a second step 804, an n-type window layer can be deposited over the substrate structure including the previously applied TCO layer and base layer. The n-type window layer may include an n-type CdS semiconductor, or an n-type CdSSe semiconductor, or may be omitted. In an optional third step 806, an interfacial layer can be deposited over the substrate structure including the previously applied n-type window layer, TCO layer, and base layer. The interfacial layer may include an n-type CdSSe semiconductor or a CST p-type semiconductor, or both semiconductors formed in sequence. In a fourth step 808, a p-type absorber layer can be deposited over the substrate structure including the optional interfacial layer(s), n-type window layer, TCO layer and base layer. The p-type absorber layer may include a p-type CdTe semiconductor, p-type CST semiconductor, or p-type CdSeTe semiconductor. In a fifth step 810, an activation process may be performed on the formed layers. In a sixth step 812, a metal back contact can be formed over the activated p-type absorber layer.

A step of the method of manufacturing a photovoltaic structure may include an expanded process as depicted in FIG. 9. The expanded process may be substituted for any step requiring the formation of a CdSSe layer, regardless whether window layer or interfacial layer, or the formation of a CdSeTe, or other layer comprising the deposition of a ternary (three-element) or quaternary (four-element) compound. In a first step 901 of the expanded process, a first precursor layer, for example CdS, is deposited over a substrate structure. In a second step 903 of the expanded process, a second precursor layer, for example cadmium selenide (CdSe), is deposited over the first precursor layer. In a third step 905 of the expanded process, the deposited precursor layers are annealed to form desired final layer form, for example CdSSe.

As noted, in one embodiment of the expanded process, the first step includes depositing a CdS layer as the first precursor layer over a substrate structure including a TCO layer and a base layer. The second step includes depositing a CdSe layer as the second precursor layer over the CdS layer. The third step includes annealing the deposited precursor layers to form a CdSSe layer of the desired CdS_(1−x)Se_(x) compositional ratio. In an alternative embodiment of the expanded process, the first CdS precursor layer is deposited over a substrate structure including an additional n-type CdS window layer, TCO layer and a base layer. In a further alternative embodiment of the expanded process, the annealing of the precursor layers occurs during the subsequent deposition of a p-type CdTe absorber layer.

Subsequent to formation of the layers, the photovoltaic structure may go through an activation process. When a CdTe, CST, or CdSeTe, or other absorber layer is used, the activation step can include the introduction of a material containing chlorine to the semiconductor bi-layer, for example cadmium chloride (CdCl₂) as a bathing solution, spray, or vapor, and an associated annealing of the absorber layer at an elevated temperature. For example, if CdCl₂ is used, the CdCl₂ can be applied over the absorber layer as an aqueous solution at a concentration of about 50 to about 500 g/L. Alternatively, the absorber layer can be annealed with CdCl₂ by continuously flowing CdCl₂ vapor over the surface of the absorber layer during the anneal. Alternative chlorine-doping materials can also be used such as MnCl₂, MgCl₂, NHCl2, ZnCl2, or TeCl2. A typical anneal can be performed at a temperature of about 350°-450° C. for a total duration of 90 minutes or less, with a soaking time equal to or less than about 60 minutes.

Inclusion of the CdSSe layer can serve to protect the CdS window layer, if included as an interfacial layer between the CdS and the CdTe layers, during the activation step thus preventing the CdS material of the window layer from excessively intermixing into the into the CdTe layer. As a result, more aggressive activation conditions (e.g., more CdCl₂ dopant and/or higher annealing temperatures and/or longer annealing durations) can be used in order to improve the CdTe absorber layer without affecting the integrity of the CdS material of the window layer. For example, when the interfacial layer is included, a higher temperature anneal of about 415° C. to about 485° C. for a CdCl₂ activation can be used (with or without a corresponding shortened anneal time) or the duration of the anneal can be lengthened (with or without a corresponding temperature increase), while also increasing the amount of Cl applied if desired.

For each of the embodiments describing various PV stacks incorporating a CdSSe, or CdSeTe layer above, multi-step activation processes or single activation steps may be used. With each desired activation mechanism such as semiconductor grain growth, chlorine diffusion, sulfur and selenium inter-diffusion into the layers, a different thermal activation energy is required. Using a multi-step process allows each activation mechanism to be optimized.

As an example of a multi-step activation process, CdCl₂ can be applied in a single step followed by annealing using a multi-step temperature profile. For example, the anneal temperature may be ramped up to 425° C. first, held there for a period of time (e.g. 1-10 minutes) and then ramped up further to 450°-460° C. and held there for an additional period of time (e.g., 1-10 minutes) before ramping the anneal temperature back down. This temperature profile for the above anneal results in different crystallinity characteristics of the CdTe material than those of a device activated in a single anneal step at 425° C. or alternatively at 450°-460° C. As an extension or alternative to this approach, multiple CdCl₂ applications, each paired with annealing at varied times and temperatures may also be used to achieve desired layer characteristics.

In addition, during the activation step, the CdSSe layer, when used either as the window layer or as an interfacial layer between a CdS window layer and a CdTe absorber layer, may diffuse into the CdTe absorber layer, thereby forming a graded CdS_(x)Te_(y)Se_(z) layer at the interface between the interfacial layer and the absorber layer, where 0<x<1, 0≦y<1, 0<z<1 at %.

From the foregoing description, one ordinarily skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications to the invention to adapt it to various usages and conditions. 

What is claimed:
 1. A process for manufacturing a photovoltaic structure comprising: forming a cadmium sulphoselenide layer over a substrate structure; and forming a p-type absorber layer over the cadmium sulphoselenide layer, wherein the p-type absorber layer comprises cadmium and tellurium; wherein the method comprises depositing a cadmium sulphotelluride interfacial layer over the cadmium sulphoselenide layer and then forming the p-type absorber layer over the cadmium sulphotelluride layer; wherein the cadmium sulphoselenide layer is formed by one of: closed space sublimation, sputtering, vapor transport deposition, atomic layer deposition, and chemical bath deposition; the process further comprising a step of annealing at an elevated temperature to create a compound region containing cadmium, sulfur, tellurium, and selenium in CdS_(x)Te_(y)Se_(z) where 0<x<1, 0<y<1, and 0<z<1 at %.
 2. A process for manufacturing as in claim 1, further comprising the first step of depositing an n-type semiconductor window layer over a substrate structure and then performing the step of forming a cadmium sulphoselenide layer over the substrate structure.
 3. A process for manufacturing as in claim 1, where the step of forming the cadmium sulphoselenide layer includes co-evaporating blended cadmium sulfide powder and cadmium selenide powder.
 4. A process for manufacturing as in claim 1, where the step of forming the cadmium sulphoselenide layer includes evaporating pre-alloyed cadmium sulphoselenide powder.
 5. A process for manufacturing a photovoltaic structure comprising: forming a cadmium sulphoselenide layer over a substrate structure; and forming a p-type absorber layer over the cadmium sulphoselenide layer; wherein the cadmium sulphoselenide layer is formed by one of: closed space sublimation, sputtering, vapor transport deposition, atomic layer deposition, and chemical bath deposition; and where the step of forming the cadmium sulphoselenide layer includes: forming a cadmium sulfide layer, forming a cadmium selenide layer, and annealing the cadmium sulfide and cadmium selenide layers to form cadmium sulphoselenide.
 6. A process for manufacturing as in claim 5 where the step of annealing the cadmium sulfide and cadmium selenide layers occurs concurrently with the step of forming a p-type absorber layer over the cadmium selenide layer. 